Pin 4 seems to be /MCLR = Master Clear = Reset on most PIC datasheets I've seen.This is what I see on my dongul pic with a logic probe /multimeter
01 <=> dead
02 <=> dead
03 <=> dead
04 <=> Pulse a little after boot then goes LOW / PIN 116 on Vrender0
05 <=> LOW / GND
06 <=> dead
07 <=> dead
08 <=> dead
09 <=> dead
10 <=> dead
11 <=> dead
12 <=> dead
13 <=> dead
14 <=> HIGH / VCC (3.5V measured)
15 <=> LOW / clock? 100ohm between pin and upper clock pin
16 <=> dead
17 <=> Pulse a little after boot then goes LOW / PIN 113 on VRender0
18 <=> dead
Pin 17 is RA0 = bit 0 of port A
Pin 15 is OSC2/CLKOUT
(Pin 16 should be OSC1/CLKIN)
These pins are actually identical on many PIC variants of that package size, the differences are in amount of Program FLASH, RAM and peripherals.
Of course, if the main cpu just boots whatever it has got if the PIC is not found then we can use brizzo's information to build a cart around pre-patched games.

Another problem will be memory chips: The original cartridges use Intel E28F128J3A (128 MBit, 16MB) 3V Flash chips which don't seem to be in stock at big distributors. You can get them for silly prices on eBay, or from smaller resellers on dodgy websites. There are bigger flash chips available from other vendors, but someone will have to dig out the datasheets and see what is usable.